US6268532B1 - Sulfonated perfluorovinyl functional monomers - Google Patents

Sulfonated perfluorovinyl functional monomers Download PDF

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Publication number
US6268532B1
US6268532B1 US09/586,844 US58684400A US6268532B1 US 6268532 B1 US6268532 B1 US 6268532B1 US 58684400 A US58684400 A US 58684400A US 6268532 B1 US6268532 B1 US 6268532B1
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monomer
mol
product
mixture
bromotetrafluoroethoxy
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US09/586,844
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Darryl D. DesMarteau
Charles W. Martin
Lawrence A. Ford
Yuan Xie
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3M Innovative Properties Co
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3M Innovative Properties Co
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Assigned to 3M INNOVATIVE PROPERTIES COMPANY reassignment 3M INNOVATIVE PROPERTIES COMPANY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: MARTIN, CHARLES W., XIE, YUAN, DESMARTEAU, DARRYL D., FORD, LAWRENCE A.
Priority to US09/586,844 priority Critical patent/US6268532B1/en
Priority to JP2002501821A priority patent/JP4414135B2/ja
Priority to CA002407644A priority patent/CA2407644A1/en
Priority to PCT/US2000/025589 priority patent/WO2001094305A1/en
Priority to DE60010936T priority patent/DE60010936T2/de
Priority to EP00966743A priority patent/EP1286961B1/en
Priority to AT00966743T priority patent/ATE267165T1/de
Priority to AU2000277040A priority patent/AU2000277040A1/en
Priority to KR1020027016520A priority patent/KR100719414B1/ko
Priority to US09/827,990 priority patent/US6384167B2/en
Publication of US6268532B1 publication Critical patent/US6268532B1/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F16/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F16/12—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
    • C08F16/32—Monomers containing two or more unsaturated aliphatic radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/78—Halides of sulfonic acids
    • C07C309/86—Halides of sulfonic acids having halosulfonyl groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C309/87—Halides of sulfonic acids having halosulfonyl groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing singly-bound oxygen atoms bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
    • C07C311/48—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups having nitrogen atoms of sulfonamide groups further bound to another hetero atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/04—Systems containing only non-condensed rings with a four-membered ring

Definitions

  • This invention relates to sulfonated perfluorovinyl monomer compositions, methods for making same, and polymers made from them.
  • Perfluorinated allyl vinyl ethers have been described, for example in U.S. Pat. No. 4,337,211 that describes alkyl fluorocarbon ethers and methods for preparation thereof, and U.S. Pat. No. 4,358,412 that describes methods for preparation of alkyl vinyl ether monomers.
  • U.S. Pat. No. 5,264,508 describes polymers and copolymers prepared from diunsaturated mono- or poly-perfluoro or haloperfluoro ethers. One site of unsaturation is used in the polymerization, resulting in a melt-processable polymer. The second site of unsaturation is then available to crosslink the polymer giving a thermoset polymer.
  • the copolymerization monomers said to be useful include “virtually any ethylenically unsaturated monomer capable of polymerization.” (col. 5 lines 31-32). Phenyl and naphthyl radicals may be included in an ether used in the copolymerization, and these radicals may include substituent groups such as a halogen or —SO 2 F.
  • U.S. Pat. No. 5,449,825 describes a method of preparation of perfluoro and haloperfluoro ethers, diethers and polyethers containing vinyl unsaturation, or allyl and vinyl unsaturation.
  • U.S. Pat. No. 5,023,380 describes compounds having two or more perfluorovinyl groups, along with their polymerization. Sulfur and sulfur-containing groups may be in the backbone of these materials. A hydrocarbyl group in the backbone must be either unsubstituted or inertly substituted, which is said to include sulfide, sulfoxide, and sulfone.
  • WO 99/38842 describes perfluorovinylbenzene sulfonyl fluoride as a precursor to a polymer. It also describes polyimide-type aromatic polymers of sulfonated sulfone polyethers, and mono- and bi-functional monomers that can have sulfur-containing backbones or substituents.
  • WO 97/25369 describes several composite membranes that include various trifluorostyrene, substituted trifluorostyrene, and ethylene-based monomers.
  • WO 99/05126 describes perfluorovinyl ionic compounds and polymers made using them.
  • the formulas described include perfluorovinyloxy substituents on a pentacyclic group and a backbone containing an aromatic group having one or more substitutents in addition to a sulfonyl group.
  • the present invention provides a monomer having the formula A—B, wherein A is represented by Formula I:
  • B is selected from —OCF ⁇ CF 2 and —A; wherein, when B is —OCF ⁇ CF 2 , the orientation of B is meta or para to the trifluorovinyloxy group of A; wherein, when B is A, the bond joining the A groups is para to the trifluorovinyloxy group of each A; and wherein each Z is independently selected from —SO 2 F, —SO 2 Cl, —SO 3 H, —SO 2 —N(M)—SO 2 CF 3 , and —SO 2 —N(M)—SO 2 R f ; wherein M is any suitable cation and R f is a C1 to C10 fluorocarbon or fluorinated ether group.
  • the present invention also provides a monomer according to Formula II:
  • X is F, Cl, or N(M)SO 2 R f , wherein M is any suitable cation and R f is a C1 to C10 fluorocarbon or fluorinated ether group.
  • substituted when used without reference to a particular substituent, means substituted by conventional substituents which do not interfere with the desired product or process, e.g., substituents can be alkyl, alkoxy, aryl, phenyl, halo (F, Cl, Br, I), cyano, nitro, etc. Also, “C(number)” refers to a chemical moiety containing the indicated number of carbon atoms.
  • Such monomers are useful in preparing polymers such as described in copending U.S. patent application Ser. No. 09/589,522.
  • Such polymers can have desirable mechanical properties along with a desirable level of ionic conductivity.
  • block copolymers having sulfonated and non-sulfonated blocks can be prepared.
  • the ionic conductivity of the resultant polymer can be controlled.
  • the block proportions of one or more other monomers the mechanical properties of the resultant polymer can be controlled.
  • the present invention provides perfluorovinyl monomers comprising sulfonated units and methods for making them.
  • the present invention also provides polymers comprising the monomers having sulfonated units. These monomers have at least two trifluorovinyloxy groups that are attached to one or more aryl groups.
  • A The general form of the monomers of the present invention is A—B.
  • the first portion, A is represented by Formula I, shown above, with an open valence to a B group.
  • A includes a core aryl group with a trifluorovinyloxy group and a separate group defined by Z.
  • B is either —OCF ⁇ CF 2 , or a second A group.
  • B is a second trifluorovinyloxy group
  • the core aryl group has two trifluorovinyloxy substituents that are either meta or para to each other.
  • B is a second A group
  • the trifluorovinyloxy group of each A group is para to the bond connecting the two A groups.
  • Z is independently selected from sulfur-containing subgroups, for example, —SO 2 F, —SO 2 Cl, —SO 3 H, —SO 2 —N(M)—SO 2 CF 3 , and —SO 2 —N(M)—SO 2 R f , wherein M is any suitable cation and R f is a C1 to C10 flurorocarbon or fluorinated ether group.
  • M is any suitable cation
  • R f is a C1 to C10 flurorocarbon or fluorinated ether group.
  • Z is ortho or meta to the —OCF ⁇ CF 2 group of portion A.
  • M is any suitable cation, such that it does not interfere with polymerization and that it is exchangeable with other cations, particularly H + .
  • suitable cation such that it does not interfere with polymerization and that it is exchangeable with other cations, particularly H + .
  • examples include H + , alkali metals, and R 4 N + where R 4 is a C1-C10 saturated alkyl group.
  • R f can be any suitable C1 to C10 fluorocarbon or fluorinated ether group.
  • fluorocarbons having the formula C n F 2n+1 wherein n is an integer from 1 through 10.
  • fluorinated ether groups include CF 3 (CF 2 ) y OCF 2 CF 2 —, wherein y is an integer from 1 through 7, and R k —CH 2 OCF 2 CF 2 —, wherein R k is CF 3 or C m F 2m+1 with m being an integer from 1 through 7.
  • Another monomer of the present invention comprises a reaction product of a tris(trifluorovinyloxy aryl) alkane, such as 1,1,1-tris(4′-trifluorovinyloxyphenyl)ethane, and a sulfonated trifluorovinyloxyaryl monomer.
  • a tris(trifluorovinyloxy aryl) alkane such as 1,1,1-tris(4′-trifluorovinyloxyphenyl)ethane
  • a sulfonated trifluorovinyloxyaryl monomer such as 1,1,1-tris(4′-trifluorovinyloxyphenyl)ethane
  • any suitable reaction conditions and equipment may be used to prepare the monomers of the present invention, including batch or continuous processes. Suitable conditions and equipment disclosed in the examples section below may be used.
  • a base material having the target phenyl groups is reacted to replace the hydrogen on the substituent phenyls with an alkali metal.
  • a halo-tetrafluoro alkane is substituted for the alkali metal.
  • the halotetrafluoroalkane-substituted intermediate is then sulfonated, such as with a halosulfonic acid.
  • This reaction product is neutralized, dried, and purified.
  • the material is fluorinated by substituting fluorine for the halo in the halosulfonic acid substituent.
  • a dehalogenation process converts the halotetrafluoroalkane substituent to the desired trifluorovinyloxy group.
  • the monomers of the present invention may be polymerized by any suitable method. Polymerization involves joining trifluorovinyl groups of the monomer molecules to form linking perfluorocyclobutylene (PFCB) groups.
  • PFCB perfluorocyclobutylene
  • the monomers of the present invention may be copolymerized with any suitable co-monomer or co-monomers. Heating is a preferred method of polymerization of the monomers or monomer mixtures.
  • Desirable properties may be obtained by controlling the relative amounts of the sulfonated monomer or monomers and non-sulfonated monomers. Higher quantities of sulfonated monomer tend to result in higher ionic conductivity in the resultant polymer, at the expense of lower mechanical properties.
  • non-sulfonated monomers such as di(trifluorovinyloxy)aromatic monomers, CF 2 ⁇ CFO—Ph—OCFC ⁇ F 2 , (CF 2 ⁇ CFO—Ph—) 2 , and 1,1,1-tris(4′-trifluorovinyloxyphenyl)ethane, the electrical and mechanical properties of the polymer can be targeted for a particular use. These monomers are therefore useful in preparing polymers having properties desirable for ion-exchange membranes.
  • This example illustrates the preparation of a monomer of the present invention.
  • reaction product was then dried thoroughly at 140-150° C. with fill vacuum (10 ⁇ 2 torr) for at least 2 days. Then, a solution of 104 g (0.4 mol) of 1,2-dibromotetrafluoroethane in 100 mL of well-dried DMSO was transferred to the flask via a closed system. The mixture was stirred at 35-40° C. for 4 days, followed by filtration to remove the solid precipitate. The precipitate was washed with acetone three times.
  • the solution was filtered to remove the solid materials and the filtrate was diluted with 150 mL of methylene chloride, and refluxed with active carbon overnight.
  • the crude product was purified by column chromatography (silica gel, 70-230 mesh, from Aldrich Chemical Co.) using 2 parts by volume petroleum ether to 1 part by volume chloroform as eluant.
  • the product was 4,4′-di(trifluorovinyloxy)-3,3′-biphenyldisulfonyl fluoride.
  • This example illustrates the preparation of a monomer of the present invention.
  • the dried salt and 80 mL of dry DMSO were transferred to a 250 mL stainless steel cylinder containing a stirring bar in a dry box, followed by transferring 62.4 g (0.24 mol) of 1,2-dibromotetrafluoroethane via vacuum line to the cylinder.
  • the mixture was stirred at 50° C. for 4 days.
  • the cylinder was cooled to room temperature (23° C.), and the contents of the cylinder were poured into a 100 mL beaker.
  • a sample of bulk solution was taken for 19 F NMR; the spectrum of this sample showed that the reaction at nearly 40% conversion and the amount of hydrogen by-product was about 4.8%.
  • the bulk solution was filtered and tested as neutral at this stage.
  • This example illustrates the preparation of a monomer of the present invention.
  • the crude product was purified by distillation under reduced pressure with an oil bath at a temperature of 100-110° C.
  • a total of 64 g (0.136 mol) of 1,3-di(2-bromotetrafluoro ethoxy)benzene was obtained in 80.4% yield, which had a boiling point of 76-80° C. (at 10 ⁇ 2 torr).
  • the amount of hydrogen by-product in the product was about 5.4%.
  • This example illustrates the preparation of a monomer of the present invention.
  • the crude product was purified by first acidification, and then vacuum sublimation (10 ⁇ 2 torr) to remove the excess CF 3 SO 2 NH 2 and finally converted back to its salt form by neutralization with 0.20M NaOH.
  • a total of 1.92 g (0.0019 mol) of precursor 4A was obtained as white solid in 95% yield after removing water at 10 ⁇ 2 torr while heating at 100° C.
  • This example illustrates the preparation of a monomer of the present invention.
  • a sample of 3,5-dihydroxybenzene sulfonic acid sodium salt was dried at 130° C/full vacuum for two days to the form of sodium salt dihydrate: 3,5-(HO) 2 C 6 H 3 SO 3 Na—2H 2 O.
  • a sample of 4.90 g (0.0217 mol) of the dried material were dissolved in 20 mL of DMSO, and the solution was purged with nitrogen gas for 2-3 hours. Then 20.17 mL of 2.15M KOH-water solution(0.0434 mol) was added to the solution dropwise with the reaction vessel resting in an ice-bath and under nitrogen gas. After addition of KOH solution, the reaction mixture was brought to 100° C. and stirred for one day.
  • the salt was dried thoroughly at 130° C./at 10 ⁇ 2 torr vacuum for 2 days.
  • the dried salt and 40 mL of dry DMSO were transferred to a 250 mL stainless steel cylinder containing a stirring bar in dry box, followed by transferring 20.8 g (0.08 mol) of 1,2-dibromotetrafluoroethane via vacuum line to the cylinder.
  • the mixture was stirred at 50° C. for 4 days.
  • the cylinder was cooled to room temperature, and the contents of the cylinder were poured into a 100 mL beaker.

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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US09/586,844 2000-06-05 2000-06-05 Sulfonated perfluorovinyl functional monomers Expired - Lifetime US6268532B1 (en)

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Application Number Priority Date Filing Date Title
US09/586,844 US6268532B1 (en) 2000-06-05 2000-06-05 Sulfonated perfluorovinyl functional monomers
AT00966743T ATE267165T1 (de) 2000-06-05 2000-09-18 Sulfonierte perfluorvinylfunktionalisierte monomere
CA002407644A CA2407644A1 (en) 2000-06-05 2000-09-18 Sulfonated perfluorovinyl functional monomers
PCT/US2000/025589 WO2001094305A1 (en) 2000-06-05 2000-09-18 Sulfonated perfluorovinyl functional monomers
DE60010936T DE60010936T2 (de) 2000-06-05 2000-09-18 Sulfonierte perfluorvinylfunktionalisierte monomere
EP00966743A EP1286961B1 (en) 2000-06-05 2000-09-18 Sulfonated perfluorovinyl functional monomers
JP2002501821A JP4414135B2 (ja) 2000-06-05 2000-09-18 スルホン化過フルオロビニル官能性モノマー
AU2000277040A AU2000277040A1 (en) 2000-06-05 2000-09-18 Sulfonated perfluorovinyl functional monomers
KR1020027016520A KR100719414B1 (ko) 2000-06-05 2000-09-18 술폰화 퍼플루오로비닐 관능성 단량체
US09/827,990 US6384167B2 (en) 2000-06-05 2001-04-06 Sulfonated perfluorovinyl functional monomers

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EP (1) EP1286961B1 (enExample)
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KR (1) KR100719414B1 (enExample)
AT (1) ATE267165T1 (enExample)
AU (1) AU2000277040A1 (enExample)
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US20020161101A1 (en) * 2001-03-22 2002-10-31 Clemson University Halogen containing-polymer nanocomposite compositions, methods, and products employing such compositions
US20040023016A1 (en) * 2002-08-02 2004-02-05 Cernohous Jeffrey J. Fluorinated polymers
US6689855B2 (en) 2000-06-27 2004-02-10 Clemson University Diffraction devices and methods
US6953653B2 (en) 2001-08-30 2005-10-11 Clemson University Fluoropolymer compositions, optical devices, and methods for fabricating optical devices
US20070238856A1 (en) * 2006-04-05 2007-10-11 Moore David R Trifluorovinyloxy monomers and polymers
US7632916B2 (en) 2002-08-02 2009-12-15 3M Innovative Properties Company Process to modify polymeric materials and resulting compositions
US20100121025A1 (en) * 2008-11-13 2010-05-13 E.I. Du Pont De Nemours And Company Fluorosulfonates

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US7534836B2 (en) * 2005-07-01 2009-05-19 Bausch & Lomb Incorporated Biomedical devices
US7582704B2 (en) * 2005-07-01 2009-09-01 Bausch & Lomb Incorporated Biomedical devices
US7538160B2 (en) * 2005-07-01 2009-05-26 Bausch & Lomb Incorporated Trifluorovinyl aromatic containing poly(alkyl ether) prepolymers
US7425600B2 (en) * 2005-07-01 2008-09-16 Bausch & Lomb Incorporated Polymerization products and biomedical devices containing same
US7402634B2 (en) * 2005-07-01 2008-07-22 Bausch And Lamb Incorporated Perfluorocyclobutane copolymers
US20070099054A1 (en) * 2005-11-01 2007-05-03 Fuller Timothy J Sulfonated-perfluorocyclobutane polyelectrolyte membranes for fuel cells
US8492460B2 (en) * 2006-07-28 2013-07-23 GM Global Technology Operations LLC Fluorinated polymer blocks for PEM applications
US8030405B2 (en) * 2008-05-09 2011-10-04 GM Global Technology Operations LLC Blended PEM's with elastomers for improved mechanical durability
US7897693B2 (en) * 2008-05-09 2011-03-01 Gm Global Technology Operations, Inc. Proton conductive polymer electrolytes and fuel cells
US7897692B2 (en) 2008-05-09 2011-03-01 Gm Global Technology Operations, Inc. Sulfonated perfluorocyclobutane block copolymers and proton conductive polymer membranes
US7888433B2 (en) * 2008-05-09 2011-02-15 Gm Global Technology Operations, Inc. Sulfonated-polyperfluoro-cyclobutane-polyphenylene polymers for PEM fuel cell applications
US7897691B2 (en) * 2008-05-09 2011-03-01 Gm Global Technology Operations, Inc. Proton exchange membranes for fuel cell applications
US7985805B2 (en) * 2008-05-09 2011-07-26 GM Global Technology Operations LLC Polyelectrolyte membranes comprised of blends of PFSA and sulfonated PFCB polymers
US7976730B2 (en) * 2008-08-25 2011-07-12 GM Global Technology Operations LLC Blends of low equivalent molecular weight PFSA ionomers with Kynar 2751
US9539568B2 (en) 2011-04-07 2017-01-10 Solvay Specialty Polymers Italy S.P.A. Process for the preparation of cross-linked fluorinated polymers
US9370750B2 (en) 2012-08-30 2016-06-21 GM Global Technology Operations LLC Polyolefin-PFCB ionomer

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